Carboxyalkyl esters of n-phosphonomethyl glycine

ABSTRACT

Carboxyalkyl esters of N-phosphonomethyl glycine and their salts and a process for their preparation are described. These esters and salts are useful as contact herbicides.

Elite States [191 1 3,868,407 Franz et al. Feb. 25, 1975 CARBOXYALKYLESTERS OF N-PHOSPHONOMETHYL GLYCINE Primary ExaminerLorraine A.Weinberger Assistant Examiner-Paul J. Killos [75] Inventors: John E.Franz Crestwood; Hans L.

Nufer, Creve oeur both of M0 Attorney, Agent, or Ftrm William T. Black,Donald W. Peterson [73] Assignee: Monsanto Company, St. Louis, Mo.

[22] Filed: Nov. 21, 1973 [21] Appl. No.: 417,858 [57] ABSTRACT [52]U.S. Cl. 260/482 R, 71/86 Carboxyalkyl esters of N-phosphonomethyl'glycine [51] Int. Cl. C07c 101/12 and h ir s l s and a process for theirpreparation are [58] Field of Search 260/482 R; 71/86 described. Th sterand salts are useful as contact herbicides.

[56] References Cited UNITED STATES PATENTS 3 Claims, No Drawings3,799,758 3/1974 Franz 71/86 CARBOXYALKYL ESTERS OF N-PHOSPHONOMETHYLGLYCINE if I e-cn at-ca c-o- (on won wherein M, M and M areindependently selected from the group consisting of hydrogen, alkalimetals, alkaline earth metal, ammonium, and organic ammonium groups.

A preferred embodiment of this invention are those compounds wherein atleast one of M, M and M" is hydrogen, alkali metal, alkaline earthmetal, ammonium or organic ammonium. Y

The novel carboxyalkyl esters of this invention are prepared by thereaction of N-phosphonomethyl glycine in a water solution with a lactonesuch as propiolactone in the presence of a based and then neutralizationof the base with hydrochloric acid. The various salts are prepared bytreating the free acid with an appropriate base.

The temperature of the reaction is normally maintained at about C.,although higher or lower temperatures are possible.

The order of addition of the reactants is critical. It is essential toadd the lactone to a basic water solution of N-phosphonomethyl glycine.For convenience and ease of isolation of the product, the carboxyalkylester, it is preferred to employ equal molar amounts of the lactone andN-phosphonomethyl glycine.

The reaction is normally conducted at atmospheric pressure althoughsuper-atmospheric and subatmospheric pressures may be employed.

The term alkalimetal encompasses lithium, so-

dium, potassium, cesium and rubidium; and the term alkaline earth metalincludes beryllium, magnesium, calcium, strontium and barium.

diisoamylamine, dihexylamine, di-heptylamine, dioctylamine,trimethylamine, triethylamine, tri-npropylamine, triisopropylamine,tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine,ethanolamine, n-propanolamine, isopropanolamine, diethanolamine, vN,N-diethylethanolamine, N- ethylpropanolamine, N-butylethanolamine,allylamine, n-butenyl-Z-amine, n-pentenyl-Z-amine,2,3-dimethylbutenyI-Z-amine, di-butenyI-Z-amine, n-hexenyl-2- amine andpropylenediamine.

The following examples serve to further illustrate the invention. In theexamples, all parts and percents are by weight unless otherwiseexpressly set forth.

EXAMPLE 1 Into a 500 ml. round bottomed flask was charged N-phosphonomethyl glycine 17 g.), water (200 ml.) and sodium hydroxide (12g.) and the mixture stirred until a clear solution was obtained. Thesolution was cooled to 20C. and propiolactone (8 g.) was added over a 15minute period with stirring. The stirring was continued for 1 hour atroom temperature. The reaction mixture was acidified with hydrochloricacid during which time a solid formed to give an aqueous slurry. Thesolid was removed by filtration and dried. The solid was identifled as2-carboxyethyl-N-phosphonomethyl glycinate (Compound l),(m.p. 211C. withdecomposition) and gave the following elemental analysis:

CALCU- FOUND LATED C 29.79% 29.78% H 5.33% 5.08% N 5.79% 5.71% P 12.80%l2.63%

' EXAMPLE 2 A water solution of the bis(isopropylamine)salt of 2-carboxyethyl-N-phosphonomethyl glycinate was prepared as follows:

2-Carboxyethyl-N-phosphonomethyl glycinate (4.04 g.) was slurried inwater (5.0 g.). To the mixture, with cooling, was added isopropylamine(1.92 g.) was added, yielding a water solution containing thebis(isopropylamine)salt of 2-carboxyethyl-N- phosphonomethyl glycinate(Compound ll).

EXAMPLE 3 The spray, a water solution containing the active ingredientand a surfactant (35 parts butylamine salt of dodecylbenzene sulfonicacid and 65 parts tall oil condensed with ethylene oxide in the ratio ofl 1 moles ethylene oxide to 1 mole tall oil) is applied to the plants indifferent sets of pans at several rates (pounds of active ingredient peracre). The treated plants are placed in a greenhouse and the effects areobserved and recorded after approximately 2 weeks or approximately 4weeks as is indicated in the table.

The post-emergence herbicidal index used in the table is as follows:

phosphonomethylglycinate Monoaodium salt of phonomethylglycinatePotassium salt of Z-carboxyethyl-N-phosphonomethylglycinateMono(dialkylamine) salts of 2-carboxyethyl-N-phosphonomethylglycinateZ-carboxyethyl-N-phos- Monolithium salt of Z-carboxyethyl-N-phosl5 PLANTRESPONSE INDEX phonomethylglycinate No 0 Trisodium salt of2-carboxyethyl-N-phosphonomesligmjhgny l thylglycmate Moderate Injury 2Monocesium salt of 2-carboxyethyl-N-phos- 21:2 InJury 2 h m h ys nsts 7.

TABLE I Observed Rate Mom- Lambs- Weeks Comlb/ Canada Cockle-Velvetingquar- Smart- Nuts- Quack- Johnson- Bromus Barnyard After poundacre Thistle bur leaf glory ters weed edge grass grass Tectorum GrassTreatment I 4 l 0 l 3 0 O l 0 O 3 2 l 0 l 3 0 O l O l 3 4 ll l0 3 3 2 23 l l 2 2 2 2 3 3 3 3 3 2 2 2 3 3 4 4 l l l 2 3 2 O 0 l 0 l 2 l l l 2 42 O O 0 O 2 4 Ill 10 2 2 2 2 2 O 2 O 2 2 3 2 3 2 2 2 3 0 2 l 3 3 3 4 4 2l 2 2 2 l O O l l 2 2 2 l 2 2 2 2 0 l l l 3 4 v For the sake of brevityand simplicity, the term active ingredient is employed hereinafter inthis specification to describe the carboxyalkyl ester of N-phosphonomethyl glycine derivatives of this invention,

. hereinbefore described.

In herbicidal compositions, the active ingredient can Dipotassium saltof 2-carboxyethyl-N-phosphonomethylglycinate Tripotassium salt ofphonomethylglycinate Monocyclohexylamine salt of 2-carboxyethyl-N-phosphonomethylglycinate 2-carboxyethyl-N-phos- Di(methylamine) salt of2-carboxyethyl-N-phosbe admixed with one or more adjuvants which can bephonomethylglycinate solid or liquid extenders, carriers, diluents.condition- Di(dimethylamine) salt of Z-carboxyethyl-N-phosing agents andthe like. The herbicidal formulations phonomethylglycinate comprisewettable powders, aqueous suspensions, dust Di(ethylamine) salt of2-carboxyethyl-N-ph0sformulations, emulsifiable oils and solutions insolvents. In general, these formulations can all containphonomethylglycinate Di(n-propylamine) salt ofZ-carboxyethyl-N-phosphonomethylglycinate Di(iso-butylamine) salt ofphosphonomethyl glycinate Mono (oleylamine) salt of2-carboxyethyl-N-phosphonomethylglycinate Mono (steaylamine) salt of2-carboxyethyl-N-phosphonomethylglycinate Mono (tallowamine) salt of2-carboxyethyl-N-phosone or more surface-active agents.

Surface-active agents which can be used in herbicidal formulations arewell known to those skilled in the art and have been well documented inUS. Patents, bulletins and textbooks.

The preparation, formulations and particle size of the wettable powders,aqueous suspensions, dusts, emulsi' fiable oils and solutions insolvents are also well known to those skilled in the art and welldocumented.

2-carboxyethyl-N- phonomethylglycinate The active ingredient is usuallypresent in the herbi- Mono(methylbutylamme) Salt of Y Y cidalcompositions in a range of about 0.5 to parts phosphonomethylglycmate byweight per parts by weight of wettable powder and dust formulations; 5to 95 parts by weight per 100 EXAMPLE 4 65 parts by weight emulsifiableoil formulations. Formulations containing other than the abovequantities of active ingredient can easily be prepared by those skilledWilmett- The post-emergent herbicidal activity of the compounds of thisinvention is demonstrated as follows. saq sjnst d snts as p i i Spray fr 9 Application of the herbicidal compositions of this invention to theplant is well-known to those skilled in the art. The application ofliquid and particulate solid herbicidal formulations to the above-groundportions of plants can be carried out by conventional methods, e.g.,power dusters, boom and hand sprayers and spray dusters.

The active ingredient can be admixed with one or more adjuvants whichcan be solid or liquid extenders, carriers, diluents, conditioningagents and the like to form herbicidal compositions. Herbicidalformulations contain the active ingredients of this invention withwettable powders, aqueous suspensions, dust formulations, emulsifiableoils and solutions in solvents. In general, these formulations can allcontain one or more surface-active agents. Herbicidal mixtures areapplied at a rate of l to 50 parts per acre of active ingredient forgeneral herbicidal effect.

While the illustrative embodiments of the invention have been describedherein before with particularity, it will be understood that variousother modifications will be apparent to and can readily be made by thoseskilled in the art without departing from the scope and spirit of theinvention. According, it is not intended that the scope of the claimsappended hereto be limited to the examples and description set forthherein but rather the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present inventionincluding all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

What is claimed is:

1. A compound of the formula UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION PATENT NO. 3,868,407 DATED February 25, 1975 lNvENTORtS) JohnE. Franz and Hans L. Nufer It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

[SEAL] A nest:

RUTH C. MASON Arresting Officer Signed and Scaled this fourth Day Of May1976 C. MARSHALL DANN Commissioner of Pal-f lls and Trademarks

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1, which is Beta-carboxyethyl-N-phosphonomethyl glycinate.
 3. The compound of claim 1,which is the mono-isopropylamine salt of Beta-carboxyethyl-N-phosphonomethyl glycinate.